Diethylene triamine condensate



Patented June 1, 1954 DIETHYLENE TRIAMINE CONDENSATE Charles F. Pickett, Bel Air, and Myer Rosenfeld, Aberdeen, Md.

No Drawing. Application August 30, 1951, Serial No. 244,453

(Granted under Title 35, U. S. Code (1952), sec. 266) 5 9 Claims.

This application is a continuation-impart of our Co-pending application, Serial Number 67,083 filed December 23, 1948, now Patent No. 2,616,856, and relates to the condensation products of diethylene triamine and .diacetone alcohol. We have found that such products are useful as detergents particularly'when in a synergistic mixtur with an oleate. It is accordingly the pri mary object of the, invention to provide condensation products of diethylene triamine and diacetone alcohol suitable as ingredients for detergent compositions. Other objects of the invention will be evident hereinafter.

'Ifhe two materials forming the basis of our inventionare both-well known chemicals of commerce and the. commercially available products are enfiirelysuitable for our purpose. Diethylene triamine,2,,2.-diaminodiethylamine,. is a. strongly alkaline, hygroscopic, somewhat viscous liquid with, the formula NI-IzCzI-I4NHC2H4NH2, a boiling point of'207.1 C. and a specific gravity of 0.9542 at- 20 0120. Commercial specifications tolerate a specific gravity of ;953'-0-.958' at 20 (Lt/20" C; and-a boiling range of-18521 C. at 760' mm. pressure; This triamine is solubl'e in water and hydrocarbons and is-used as a solvent for materials such as sulfur: and resins and as a saponification agent. for acids. Diacet'onev alcohol,- iehydroxy damethyl-a-pentanone; is a colorless liquid. with; a. boiling. point M12166? (3., a. freezing point: of ..l44 (3., specificgravityrof 0.94062 f- C.-/20 and the: formulae (CHrlzQQHCHaGQQHs.

Commercially adistillation rangeof 0; is accepted. it is miscible with alcohols; hydrocarbons; estersand water and is used in antifreeze mixtures, compression fiuids: and? in metal. cleaning compositions.

We have found that diethylene triamine; reacts readily with diacetone alcohol. in the proportions of one mole of the former with one, two or three moles of the latter to form a condensation prodnot or series of such products-of definite value as a detergent. When the diethylene triamine and-- diacetone alcohol are. simply mixed in the above proportions at ambient temperature, the reaction mixture quickly becomes warm. The condensation is very rapid and, for the purposes of theinvention, can be considered as complete after the mixtu re has been allowed to standfor' at least --onehopr; If =the-initial mixture of reagents; is "heated" to about-70 C1, the reaction proceeds'wi-th the evolution'of much heat, an indication that; as wouldbe expected, increase" in temperature has increased the reactioh'rate. When elevated temperatures are employed the precaution should be taken of adding one ma terial to the other dropwise in a flask provided with a reflux condenser. In production, water cooled kettles or reaction vessels may be utilized.

As illustrative of procedures for preparing the condensation product of our invention, the following examples are given:

Example 1.To 499 ml. (about 4 moles) of diacetone alcohol are added 21-6 ml. (about 2 moles) of diethylene triamine in about 25' m1. portions, shaking after each addition. The last four portions of diethylene triamine are added slowly to avoid a too vigorous reaction. The mixture as described contains an excess of the alcohol and may be used as prepared.- Mixtures containing stoichiometric proportions or an excess of the triamine may also-be reacted inthe same manner as shown in this example. The order of adding the reactants to each other may be reversed, i. e. the diacetone alcohol may be added to the diethylene triamine, but this order affects the product as will be shown below. Re-

-. gardless of the order of mixing the ingredients,

the product formed will synergistically cooperate with the oleate of diethylene triamine, as explained in the above mentioned co-pending application, aiter s-tandi-ngone'hour, severaldays or four weeks indicating that the cooperating condensate is formed to aconsiderable extentin the early stages of the reaction.

Example 2.-Either component in calculated quantity is slowly added at one time to the other at ambient temperature forming distinct layers of the components. In this and all the other calculations one molecular weight of diethylene triamine is taken as 1.07.6 ml. and one molecular weight of diacetone alcohol as 124.8 ml. Stirring is not used in this caseythe reaction rate being controlled by' interdiffusi'on'. After a' period of from: four-to sixteen hours the resultant mix is thoroughly stirred. The mix is'ready for use in some applications in five hours but steadily'im provesfor about sixteen. No more-than one-half gallon i'sprepared'in onebatch'to avoid excessive heat of reaction? Example 3.' =The' desired molar quantity of one component is added dropwise to the calculated quantityof the other component at ambient temperature with vigorous stirring with an air stirrer or other spark-free stirrer. If the diethylene triamine is added to' the diacetone alcc- 1101; the rate ofaddition'is twoto three milliliters" perminute'perliteroi"diacetonealcohol; If the" reverse addition order is used, the diacetone alcohol is added at the rate of 25-30 ml. per minute per liter of the diethylene triamine. After equal molar quantities have been added, very rapid addition of the remaining alcohol is possible. The temperature attained by the reacting mixes in either of these directions of addition does not usually exceed 50 C. The resulting solutions are ready for immediate use.

That some difference exists between the condensation products depending upon the order in which the reactants are added to each other is shown by the following tables in which DA represents diacetone alcohol and DT, diethylene triamine. The tables are based upon a series of experiments in which stoichiometric ratios of the reactants were added to each other according to the procedure outlined above. The molar ratios of the reactants are indicated by the numerals placed before the symbols for the reactants while the order of mixing is shown by the word to. Thus 1 DA to l DT means that one mole of diacetone alcohol was added to one mole of diethylene triamine, 1 DA being considered equivalent to 124.8 ml. diacetone alcohol. After completion of each reaction, that is after the mixture had been allowed to set for at least one hour, viscosities were taken at two different temperatures and the specific gravity of the original condensate obtained. The cooled condensate was then extracted with petroleum ether (P. E.) of a boiling point range extending from 30-55 C. Both the petroleum ether soluble and insoluble fractions were evaporated at ambient temperature to constant weight by bubbling nitrogen through them.

Viscosities and specific gravities were obtained for both fractions. Table 1 shows the number of the sample, the ingredients and the viscosities of all fractions at 77 M. Table II shows the number of the sample, the viscosities of all fractions at 130 F., and the specific gravities at 75 F.

Table I 3. Viscosity at 77 F. (Centistokes) 1. Sample 2. Mole Ratios b. P. E. 111- 0. Solomgmal soluble uble D. A 3. 54 D. T 6. 40 1 DA to 1 DT-. 179 134 215 1 DT to 1 DA 167 135 193 1 DA to 2 DT-. 57. 6 71. 6 52. 3 2 DT to 1 DA 54.2 63.0 60.0 1 DA to 3 DT 26. 5 59. 9 225.0 3 DT to 1 DA 25. 4 48.9 55. 1 2 DA t0 1 DT. 25.2 182. 7 406. 9 1 DT to 2 DA- 27.2 165. 8 252 3 DA to l DT 6. 172.8 539. 4 1 DT to 3 DA. 6. 148. 1 300 Table II 2. Viscosity at 130 F. 3. Specific Gravity at 75 (Centistokes) F.

1. Sample b P P b P P c. c. 3 E. in- E. solgg E. m- E. solgm soluble uble g soluble uble 11. 5 12. 0 18. 5 0. 984 0. 989 0. 972 11. 9 l2. 9 12. 6 981 988 975 8. 73 9. 93 8. 48 978 992 963 8. 57 9. 22 9. l3 981 989 973 5. 82 9. 51 19. 7 966 .998 984 5. 63 8. 8. 68 973 991 973 4. 76 14. 1 25. 2 948 988 982 5. 00 14. 2 l9. 8 .946 987 977 2. 17 15. 1 29. 3 917 986 987 2. 03 11. 0 22. 4 .914 973 974 T cohol to 215.2 mi. of diethylene triamine.

Sample 3 in the above tables was made by adding 124.8 ml., diacetone alcohol to 107.6 mi. diethylene triamine without stirring. After four hours the product was shaken thoroughly. Tests were made after not less than sixteen hours. Sample 4 was made in identical fashion but by addition of the diethylene triamine to the diacetone alcohol. Sample 5 was made like sample 3 but by addition of 124.8 ml. of diacetone al- All other samples were prepared similarly using the amounts and order of addition indicated by the symbolic representation of column 2, Table I.

The complexity of the reaction as well as the improbability of indicating a particular compound is readily recognized from the data. Other indications of this complexity exist. For example the colors vary from the yellow of diethylene triamine and the colorlessness of the diacetone alcohol through reddish brown, brown and dark brown in sample 12. All the condensates are useful as detergents, particularly when in synergistic relationship with the diethylene triamine oleate of the parent application. Some difference in effect can be seen, however, dependent upon the method of preparation of the condensate. If the triamine is added to the alcohol, the resultant condensate gives best results mixed with the oleate in a hydrocarbon solvent. On the other hand. the condensate formed by adding the alcohol to the triamine gives best results with water as a solvent. The condensates are soluble in water but are only soluble in oil in the presence of surfactants such as diglycol oleate, ethanol amine oleate and diethylene triamine oleate.

The obvious explanation of the condensation reaction is the splitting 01f of water by the union of the carbonyl oxygen of the diacetone alcohol with the hydrogens of one or both of the terminal amine groups of the diethylene triamine. The amount of diacetone alcohol introduced into the diethylene triamine molecule can be varied merely by changing the order in which the two reactants are added to each other. Consequently the reaction is not as straightforward as it appears on the surface. The hydroxyl group of the alcohol is perhaps rendered exceptionally active due to the presence of the adjacent carbonyl group and is replaceable by the nitrogen to some extent. Such nitrogen would be held loosely under these conditions and could be highly adsorbable on a metal surface. The adsorption energy would be very high and might be sufiicient l to cause bonding of the compound to a metal preferentially to soil bonding.

Because the methylene group of diacetone a1- cohol is attached to carbons which are attached to oxygens (carbonyl oxygen in one case, and hydroxyl oxygen in the other) it is believed that there is an enol-keto transformation:

(CH3) 2C(OH) CH=C (OH) CH3 It is obvious that the reaction is not solely a Schiffs base type, because diacetone alcohol is reacted with triethylamine which contains no hydrogen bound to the nitrogen. The explanation is believed to lie in molecule (2) above. This extensive addition of the amine.

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Whether the nitrogen bonding is weakened dueto a tertiary bonding, or only exists as a secondary linkage,'is not known. However, it is believed that part of the cleansing ability of the molecule is derived from the energy of the molecular adsorption on the surface at the nitrogen. The condensate, in any case, has been found to be very efficient when used in conjunction with other surfactants.

Referring to (3), it can be seen that there are two unreacted amine groups present. If diethylene triamine is added to diacetone alcohol, many molecules of the diacetone alcohol are available for reacting with the diethylene triamine. There are three amine groups present in the triamine and each one of these can react with diacetone alcohol. One would also expect diamine derivatives to be present, as the reactive alcohol available becomes lessened with more Such diamines and triamines might take the form of (4) and (5) respectively.

CH3C(OH) =CHC(CH3) 2N(H) (OH) [CH2CH2N(H) 2(OH) C(CHa) 2CH=C(OH) CHsh (CH3) 2C(O'H) CHzCH(OH) (6) mono-diacetone derivative (CH3) 2C(OH) CH2CH(OH) NHCH2CH2NHCH2CH2NHCH(OH) CHzC (OH) (CH3) 2 (6) (ii-diacetone derivative The important point stressedf here isfnot'ithe .particular compounds formedybut the manner in'which different types of compounds can-be expected, depending on 'order of addition. "To

reiterate, if diethylene triamine is added to diacetone alcohol, one molecule of diethylene triamine initially encounters many molecules of diacetone alcohol, so that each of the amine groups can be reacted with diacetone alcohol. This situation will continue so long as the probability is in favor of a given molecule of diethylene triamine colliding with more than one unreacted diacetone alcohol. However, when diacetone alcohol is added to the diethylene triamine, regardless of mechanism of reaction, there are many diethylene triamine molecules present per molecule of diacetone alcohol. It is, therefore, much more probable for collision of successively added diacetone alcohol molecules to be with different amine molecules, than for successive diacetone alcohol molecules to hit the same diethylene triamine molecule. When most of the mono-amine derivatives have been formed, diamines can be formed. It is obvious, however, that only a minute amount of tri-amine derivatives could be expected, in a solution in which the mole ratio of diethylene triamine to diacetone alcohol is 1:1 or 1:2, and that the rate of even diamine formation would be quite slow compared to the previous direction of addition. The logic of this reasoning is borne out by the fact that much more heat is evolved in adding the amine to the diacetone alcohol than in the reverse manner of addition. Consequently, when the preparation is made with thorough stirring, it is safe to add 25-30 ml. per minute of diacetone alcohol per liter of diethylene triamine used; however, only 2 to 3 ml. per minute of diethylene triamine can be added per liter of diacetone alcohol to the diacetone alcohol, if it is desired to keep the reaction fom becoming unduly vigorous. 1

While in the foregoing paragraphs we have (6) tri-diacetone derivative 7) mono-diacetone derivative outlined a theoretical reaction scheme, we desire to be bound solely by the appended claims.

What we claim is: l. The condensation product formed by admixing diethylene triamine and 4-hydroxy-4- 7 methyl-2-pentanone in the ratio of one mole of the diethylene triamine to from one to three moles of diacetone alcohol.

2. The condensation product formed by adding diethylene triamine stepwise to 4-hydroxy-4- methyl-Z-pentanone until the ratio of reactants is one mole of the diethylene triamine to from one to three moles of 4-hydroxy-4-methyl-2- pentanone.

3. The condensation product formed by 4- hydroxy-4-methyl-2-pentanone stepwise to diethylene triamine until the ratio of reactants is one mole of the diethylene triamine to from one to three moles of 4-hydroxy-4-methyl- 2-pentanone.

4. The condensation product formed by gradually adding from one to three mols of 4-hydroxy- 4-methyl-2-pentanone to one mol of diethylene triamine in distinct layers, permitting a condensation reaction to take place over a period of from four to sixteen hours by interdiflusion of the reactants and then thoroughly stirring the mix.

5. The reaction product obtained by reacting one mol of diethylene triamine and '3 mols of 4-hydroxy-4-methyl-2-pentanone.

6. The condensation product of diethylene triamine and 4-hydroxy-@methyl-Z-pentanone in the ratio of about one mole of diethylene triamine to from one to three mols of 4-hydroxy-4-methyl- Z-pentanone.

7. The reaction product obtained by admixing one mol of diethylene triamine with three mols of 4-hydroxy-4-methyl-2-pentanone and thereafter permitting the reaction to proceed for a period of time from about one hour to four weeks.

8. The reaction product obtained by admixing one mol of diethylene triamine with three mols of 4-hydroXy-4-methy1-2-pentanone at ambient temperature and thereafter permitting the reaction to proceed for a period of time from about one hour to four weeks.

9. The process of producing a reaction product from diethylene triamine and 4-hydroxy-4- methyl-Z-pentanone which comprises gradually bringing the reacting materials into admixture in proportions of one mole of diethylene triamine to three mols of -hydroxyi-methyl-z-pentanone and thereafter interrupting the reaction within a period of time of about one hour to four Weeks.

N 0 references cited. 

1. THE CONDENSATION PRODUCT FORMED BY ADMIXING DIETHYLENE TRIAMINE AND 4-HYDROXY-4METHYL-2-PENTANONE IN THE RATIO OF ONE MOLE OF THE DIETHYLENE TRIAMINE TO FROM ONE TO THREE MOLES OF DIACETONE ALCOHOL. 